Preparation of supramolecular polymer containing quadruple hydrogen bonding units in the polymer backbone

ABSTRACT

The present invention relates to a supramolecular polymer comprising quadruple hydrogen bonding units within the polymer backbone, wherein at least a monomer comprising a 4H-unit is incorporated in the polymer backbone via at least two reactive groups up to four reactive groups, provided that the 4H-units are not covalently incorporated in the polymer backbone through one or more silicon-carbon bonds. The invention also relates to processes for preparing such supramolecular polymers and their use in personal care applications, surface coatings, imaging technologies, biomedical applications, (thermo)reversible coatings, adhesive and sealing compositions and as thickening agents, gelling agents and binders.

This application is a United States National Phase application ofPCT/NL2003/000766, filed Nov. 4, 2003, the disclosure of which has beenincorporated by reference herein in its entirety.

FIELD OF THE INVENTION

The invention relates to supramolecular polymers comprising quadruplehydrogen bonding units within the polymer backbone. The supramolecularpolymers can be prepared by (i) chain extension or (ii) redistribution.In chain extension, a monomer containing (a precursor of) a quadruplehydrogen bonding group is copolymerized with a macromonoiner of choice,whereas in redistribution a polymer of choice is reacted with a monomercontaining a quadruple hydrogen bonding unit. The resultingsupramolecular polymers show unique new characteristics due to thepresence of additional physical interactions between the polymer chainsthat are based on multiple hydrogen bonding interactions (supramolecularinteractions).

BACKGROUND OF THE INVENTION

This invention relates to supramolecular polymers comprising quadruplehydrogen bonding units that are capable of forming at least fourH-bridges with each other leading to physical interactions betweendifferent polymer chains. The physical interactions originate frommultiple hydrogen bonding interactions (supramolecular interactions)between self-complementary units comprising at least four hydrogen bondsin a row. Units capable of forming at least four hydrogen bonds, i.e.quadruple hydrogen bonding units, are in this patent applicationabbreviated as 4H-units, 4H-elements or structural elements (4H) and areused in this patent application as interchangeable terms. Sijbesma etal. (U.S. Pat. No. 6,320,018; Science, 278, 1601; incorporated byreference herein) discloses such self-complementary units which arebased on 2-ureido-4-pyrimidones.

Telechelic polymers or trifunctional polymers have been modified with4H-units (Folmer, B. J. B. et al., Adv. Mater. 2000, Vol. 12, 874;Hirschberg et al., Macromolecules 1999, Vol. 32, 2696; Lange, R. F. M.et al, J. Polym. Sci, Part A, 1999, 37, 3657-3670). However, thesepolymers have the 4H-unit coupled at the ends of the polymers, so thenumber of end groups is therefore limited by the amount of end groups(normally 2), and the functional units are always located on theperiphery of the polymer.

Polymers containing hydrogen bonding groups grafted on the main chainthat are synthesized via copolymerization of hydrogen bonding monomershave been obtained with hydrogen bonding units containing three H-bondsin a row (Lange F. M. et al., Macromolecules 1995, Vol 28, 782).However, only an alternating copolymer of styrene and maleimide can beused in this approach, and moreover, the H-bonding interactions betweenthe polymers are much weaker than the H-bonding based on the 4H-units,obviously resulting in poorer material properties.

Polymers with quadruple H-bonding units grafted on the main chain havebeen obtained by copolymerizing an olefin bearing a 4H-unit with acommon olefin (Coates, G. W. et al., Angew. Chem. Int. Ed., 2001, Vol.40, 2153). However, complex chemistry has to be used to prepare and topolymerize the monomer and, due to the intrinsic sensitivity of thecatalyst needed to obtain the polymer, severe limitations hinder thegeneral use of this system and limits it to tailor-made polyolefinsystems. For example, Coates et al. discloses the copolymerization of1-hexene and a 6-hexenyl-2-ureido-4-pyrimidone derivative with aZiegler-Natta type nickel based catalyst and diethylaluminum chloride ascocatalyst. Another drawback of the method according to Coates et al. isthat the amount of 4H-units that can be incorporated in the copolymer israther limited, i.e. typically about 2 mol %.

WO 02/46260 discloses polyurethane based polymers with H-bonding unitsas end-cappers and optionally grafted with H-bonding units that can beused as hot melt adhesive or TPU-foam. WO 02/098377 discloses polymerswith H-bonding units as end groups that can be used in cosmeticcompositions. Both patent applications use comparable or the samechemistry as described in the papers above.

U.S. Provisional Patent Application No. 60/403,636, filed Aug. 16, 2002,and PCT/NL03/00586, filed Aug. 15, 2003, incorporated by referenceherein for the US patent practice, discloses simpler chemistry toacquire polymers with grafted quadruple H-bonding units. For example,polyacrylates and polymethacrylates with grafted 4H-units have beenproduced using different kinds of polymerization techniques.

U.S. Provisional Patent Application No. 60/431,712, filed Dec. 3, 2002,incorporated by reference herein for the US patent practice, disclosespolysiloxanes comprising 4H-units in the polymer backbone. Moreprecisely, polysiloxanes are disclosed having (a) 4H-units directlyincorporated in the polymer backbone, wherein the 4H-units areincorporated via two linkers and are covalently attached through asilicon-carbon bond or (b) 4H-units pending from the polymer backbone,wherein the 4H-units are covalently attached via one linker through asilicon-carbon bond.

The present invention discloses polymers comprising 4H-units within thepolymer backbone that can easily be prepared by chain extending afunctional macromonomer with a functional monomer comprising a 4H-unit(or a precursor of such a unit). Alternatively, redistribution reactionsof polymers with functional monomers comprising a 4H-unit can beemployed. The invention allows for control over the average amount of4H-units per polymer chain by setting the molar ratio between thereacting species.

The supramolecular according to the present invention are unprecedented,because they comprise multiple 4H-units as an integral part of thepolymeric main chain. Also, the presented supramolecular polymersdisplay unique material properties because of the reversible nature ofthe H-bonding interactions between the polymer chains, allowingreversible change of the material properties by external stimuli likeheat or dilution. Consequently, it is possible to prepare materials thatcombine the mechanical properties of conventional macromolecules withthe low melt viscosity of organic compounds. The presence of 4H-units inthe polymer backbone is strongly beneficial, because the materials areeasier to synthesize and/or result in superior material properties ascompared to polymers comprising 4H-units that have been disclosedpreviously, such as 4H-units grafted on polymers or 4H-units attached tothe end groups of polymer chains.

SUMMARY OF THE INVENTION

The invented supramolecular polymers comprise quadruple hydrogen bondingunits within the polymer backbone, wherein at least a monomer comprisinga 4H-unit is incorporated in the polymer backbone via at least tworeactive groups up to four reactive groups, preferably two to three andmost preferably two reactive groups, provided that the 4H-units are notcovalently incorporated in the polymer backbone through one or moresilicon-carbon bonds. By the term “not covalently incorporated” it ismeant that the 4H-unit is not attached to the polymer backbone by asilicon-carbon bond or by a linking moiety comprising a silicon-carbonbond.

It is even more preferred according to this invention that the inventedsupramolecular polymers comprise quadruple hydrogen bonding units withinthe polymer backbone, wherein at least a monomer comprising a 4H-unit isincorporated in the polymer backbone via at least two reactive groups upto four reactive groups, preferably two to three and most preferably tworeactive groups, with the proviso that the 4H-units are not covalentlyincorporated in the polymer backbone through one or more silicon-carbonbonds and with the proviso that the following group of supramolecularpolysiloxanes is excluded: polysiloxanes having the following generalformulae (3a) or (3b):

in which the radicals R1, that may be identical or different, areselected from substituted and unsubstituted monovalent nonaromaticethylenically free C₁-C₂₀ hydrocarbon radicals, or are selected fromaromatic radicals;

-   Q₁ and Q₂ and Q₃ are equal and denote one or more structural    elements that are capable of forming at least four hydrogen bridges    (also referred to as 4H-unit) and that are attached via a linker    through a silicon-carbon bond to the polymer; or-   Q₁ and Q₃ are equal and denote one or more 4H-units attached via a    linker through a silicon-carbon bond to the polymer and Q₂ is    defined as R1; or-   Q₁ denotes one or more 4H-units attached via a linker through a    silicon-carbon bond to the polymer and Q₂ and Q₃ are defined as R1:    or-   Q₂ denotes one or more 4H-units attached via a linker through a    silicon-carbon bond to the polymer and Q₁, and Q₃ are equal and are    defined as R1; and-   Q₄ is a 4H-unit having two linkers that are attached through a    silicon-carbon bond to the polymer chain, and m, n and c are    integers such that the mean molecular weight of the polysiloxane    ranges from 500 to 250000.

According to the present invention, the synthesis of the supramolecularpolymers involves reaction of a monomeric unit (a) that comprises a(precursor of a) 4H-element and that comprises at least two reactivegroups up to four reactive groups, preferably two to three and mostpreferably two reactive groups, with macromonomeric unit (b), preferablyhaving a number average molecular weight of at least about 100 to about100000. Different types of monomeric units (a) and macromolecular units(b) can be used in one synthetic procedure; several macromolecular units(b) can be employed wherein the macromolecular units (b) are for exampleof different chemical nature and/or of different molecular weight.

In the first embodiment of the present invention, the macromonomericunit (b) comprises at least two complementary reactive groups up to sixcomplementary reactive groups, preferably two to three complementaryreactive groups and most preferably two complementary reactive groups,and is chain extended by reaction with monomer (a) having at least twoto four reactive groups, preferably two to three reactive groups andmost preferably two reactive groups. In this patent application theterms “reactive group” and “complementary reactive group” are usedinterchangeably to indicate reactive groups that are present inmonomeric units and macromonomeric units. In this patent applicationcomplementary reactive groups are to be understood as reactive groupsthat are capable to form, preferably covalent, bonds under conventionalreaction conditions as will be apparent to a person skilled in the art.Examples of reactive groups that are complementary reactive are carboxyland hydroxyl groups that can form an ester group, carboxyl and aminegroups that can form an amide group, hydroxyl groups that can form anether group etc. However, as will be apparent to those skilled in theart, other modes of molecular bonds, e.g. ionic bonds or coordinativebonds, are within the scope of the present invention.

The resulting polymers (c) of the invention have the following generalstructure:{(a)_(p)-(b)_(q)}_(v)wherein:

-   (a) is a monomeric unit that comprises a (precursor of a)    4H-element;-   (b) is a macromonomeric unit;-   (a) and (b) are, preferably covalently, connected in the polymer    backbone;-   p and q indicate the total number of units of (a) and (b) in the    polymer backbone;-   p is 1 to 100, preferably 1 to 50 and most preferably 1 to 10;-   q is 0 to 20, preferably 1 to 50 and more preferably 1 to 20;-   ν is the number of repeating units of the connected monomeric    units (a) and the connected macromonomeric units (b);-   macromonomeric unit (b) has a number average molecular weight of at    least about 100 to about 100000, preferably about 500 to about 50000    and more preferably about 500 to about 30000; and-   polymer (c) has a number average molecular weight of about 2000 to    about 80000;-   provided that the 4H-units are not covalently incorporated in the    polymer backbone through one or more silicon-carbon bonds.

According to the invention, polymer (c) can be a homopolymer (q=0).However, it is preferred that the units (a) and (b) are both present.Units (a) and (b) can be randomly distributed along the polymer chainbut can also be alternating (i.e. that a segmented polymer is obtained).According to the present invention, it is preferred that the polymer isan alternating copolymer.

According to the second embodiment of the present invention, themacromonomeric unit (b) is a polymer of higher number average molecularweight, preferably at least about 20000 to about 100000, that can beredistributed using monomer (a). The resulting polymers (c′) have nowthe general (segmented) structure:{(a)_(p)-(b′)_(q)}_(w)wherein

-   (a) is a monomeric unit that comprises a (precursor of a)    4H-element;-   (b′) is a fragmented part of the original polymer (b);-   (a) and (b′) are, preferably covalently, connected in the polymer    backbone;-   p and q indicate the total number of units of (a) and (b) in the    polymer backbone;-   p is 1 to 100, preferably 1 to 50 and most preferably 1 to 10;-   q is 0 to 20, preferably 1 to 50 and more preferably 1 to 20;-   w is the number of repeating units of the connected monomeric    units (a) and the connected macromonomeric units (b′);-   macromonomeric unit (b′) has a number average molecular weight of at    least about 50 to about 20000, preferably about 50 to about 10000;    and-   the polymer (c′) has a number average molecular weight of about 2000    to about 80000;-   provided that the 4H-units are not covalently incorporated in the    polymer backbone through one or more silicon-carbon bonds. As will    be apparent to the person skilled in the art, the polymer (c′)    comprises fragmented parts (b′) that may have a different number    average molecular weight and/or a different molecular structure,    i.e. that not all fragmented parts (b′) need to be identical.

The number average molecular weight of the polymers according to thepresent invention are determined by size-exclusion chromatography (SEC)also known in the art as gel permeation chromatography (GPC) usingpolystyrene standards.

The supramolecular polymers according to the present invention compriseself-complementary quadruple hydrogen bonding units (4H-elements or4H-units) in the polymer backbone. The amount of 4H-units incorporatedin the polymer backbone is preferably about 33 to about 66 mol %, basedon the total amount of moles of (a) and (b) or (a) and (b′), morepreferably about 40 to about 60 mol %, and most preferably about 44 toabout 55 mol %.

According to the first embodiment of the present invention, thesynthesis of the supramolecular polymers according to the inventioninvolves reaction of a monomeric unit (a) that contains a (precursor ofa) 4H-element and that bears at least two reactive groups up to fourreactive groups, preferably two to three reactive groups and mostpreferably two reactive groups, with a macromonomeric unit (b) having atleast two complementary reactive groups up to six complementary reactivegroups, preferably two to three complementary reactive groups and morepreferably two complementary reactive groups, and wherein themacromonomeric unit (b) has a number average molecular weight of atleast about 100 to about 100000. In this first embodiment, themacromonomeric unit (b) is chain extended by reaction with monomer (a).

According to the second embodiment of the present invention, themacromonomeric unit (b) is a polymer of higher number average molecularweight, preferably at least about 20000 to about 100000, that can beredistributed using monomer (a), wherein the monomeric unit (b′) has anumber average molecular weight of at least about 50 to about 20000.

DETAILED DESCRIPTION OF THE INVENTION

Description of the Monomeric Unit (a)

Monomeric unit (a) comprises a (precursor of a) 4H-unit and severalreactive groups linked to this unit, wherein the reactive groups canform chemical bonds, preferably covalent bonds, upon reaction withmacromonomeric unit (b). In general, monomeric unit (a) can berepresented by the formulae (m) and (IV),4H-(F_(i))_(r)  (III)4H*-(F_(i))_(r)  (IV)wherein:

-   4H represents a structural element (4H):-   4H* represents a precursor of the structural element (4H):-   F_(i) represents a reactive group linked to the 4H-unit or 4H*-unit;    and-   r represents the number of reactive groups connected to the    (precursor of the) structural element (4H) and is within the range    of 1-4.

Hence, the 4H-unit may comprise up to four reactive groups F₁, F₂, F₃and F₄, provided that the 4H-unit comprises at least two of suchreactive groups.

According to the present invention, r can be from 1 to 4. According tothe present invention, r is preferably 2 or 3 and most preferably 2.

According to the present invention, the monomeric unit (a) canpreferably (r=2) be represented by the following formulae:F₁-4H-F₁ or F₁-4H-F₂ or F₁-4H*-F₁ or F₁-4H*-F₂

In general, the structural element that is capable of forming at leastfour hydrogen bridges (4H) has the general form (1′) or (2′):

If the structural element (4H) is capable of forming four hydrogenbridges which is preferred according to the invention, the structuralelement (4H) has preferably the general form (1) or (2):

In all general forms shown above the C—X_(i) and C—Y_(i) linkages eachrepresent a single or double bond, n is 4 or more and X₁ . . . X_(n)represent donors or acceptors that form hydrogen bridges with theH-bridge-forming unit containing a corresponding structural element (2)linked to them, with X_(i) representing a donor and Y_(i) an acceptor orvice versa. Properties of the structural element having general forms(1′), (2′), (1) or (2) are disclosed in U.S. Pat. No. 6,320,018 whichfor the US practice is incorporated herein by reference.

The structural elements (4H) have at least four donors or acceptors,preferably four donors or acceptors, so that they can in pairs form atleast four hydrogen bridges with one another. Preferably the structuralelements (4H) have at least two successive donors, followed by at leasttwo acceptors, preferably two successive donors followed by twosuccessive acceptors, preferably structural elements according togeneral form (1′) or more preferably (1) with n=4, in which X₁ and X₂both represent a donor and an acceptor, respectively, and X₃ and X₄ bothan acceptor and a donor, respectively. According to the invention, thedonors and acceptors are preferably O, S, and N atoms.

Molecules that can be used to construct the structural element (4H) arenitrogen containing compounds that are reacted with isocyanates,thioisocyanates or activated amines, or that are activated and reactedwith primary amines, to obtain a urea or thiourea moiety that is part ofthe quadruple hydrogen bonding site. The nitrogen containing compound ispreferably an isocytosine derivative (i.e. a2-amino-4-hydroxy-pyrimidine derivative) or a triazine derivative, or atautomer and/or enantiomer of these derivatives. More preferably, thenitrogen containing compound is an isocytosine derivative having aproton or aliphatic-substituent containing a functional group in the5-position and an alkyl-substituent in the 6-position, most preferably2-hydroxy-ethyl or propionic acid ester in the 5-position and methyl inthe 6-position, or hydrogen in the 5-position and methyl in the6-position. The isocyanates or the thioisocyanates can be monofunctionalisocyanates or monofunctional thioisocyanates or bifunctionaldiisocyanates or bifunctional thioisocyanates (for example alkyl or aryl(di)(thio)isocyanate(s)).

According to the invention, monomer (a) that contains the structuralelement (4H) is particularly suitably represented in the compoundshaving the general formulae (3) or (4), and tautomers and/or enantiomersthereof (see below). Monomer (a) that contains a precursor of thestructural element (4H), i.e. (4H*), is particularly suitablyrepresented in the compounds having the general formulae (5) or (6). TheX in formulae (4) and (6) is preferably a nitrogen atom, but it can alsobe a carbon atom with attached R4-group.

R1, R2, R3 and R4 may be hydrogen or all kinds of shorter or longerchains, for example saturated or unsaturated, branched, cyclic or linearalkyl chains, aryl chains, alkaryl chains, arylalkyl chains, esterchains, ether chains and any chain of atoms used in traditional polymerchemistry, whether or not substituted with all kinds of functionalgroups such as esters, ethers, ureas or urethanes.

It is preferred according to the present invention that the shorter orlonger chains are saturated or unsaturated, branched, cyclic or linearalkyl chains, aryl chains, alkaryl chains, alkylaryl chains, esterchains or ether chains.

Preferably, “saturated or unsaturated, branched, cyclic or linear alkylchains” denote a C₁-C₁₀ alkylene group.

“Aryl chains” preferably denote a C₆-C₁₂ arylene group.

“Alkaryl chains” and “alkylaryl chains” preferably denote a C₇-C₁₂alkaryl group and a C₇-C₁₂ alkylaryl group, respectively.

“Ester chains” preferably denote a polyester obtained by ring openingpolymerisation of C₄-C₈ lactones or dilactides or glycolides having thegeneral formula:

wherein the R groups are independently selected from the groupconsisting of linear or branched C₁-C₆ alkyl groups. However, it ispreferred that for “ester chains” the R groups are independentlyselected from hydrogen atoms and methyl groups.

“Ether chains” preferably denote a polyether chain comprising ethyleneoxide and/or propylene oxide, wherein the polyether chain is representedby the formula:—(CR**H—CR**H—O)_(w)—wherein R** can be a hydrogen atom or a methyl group and w is in therange of 10-100.

Preferably, if any one of R1-R4 comprises a reactive group (F_(i)) andis therefore a linking moiety, said linking moiety is hydrogen or aC₁-C₁₂ straight chain or branched alkylene group or a C₆-C₁₂ arylene, aC₇-C₁₂ alkarylene or a C₇-C₁₂ arylalkylene group, wherein the alkylene,arylene, alkarylene or arylalkylene group may be substituted with othergroups or may contain cyclic groups as substituent or in the main chain.Examples of such groups are methylene, ethylene, propylene,tetramethylene, pentamethylene, hexamethylene heptamethylene,octamethylene, nonamethylene, 1,6-bis(ethylene)cyclohexane,1,6-bismethylene benzene, etc. The alkylene, arylene, alkarylene orarylalkylene groups may be interrupted by heteroatoms, in particularheteroatoms selected from the group consisting of of oxygen, nitrogen,and sulphur.

However. according to the invention, it is even more preferred that thestructural elements (4H) or (4H*) in the compounds (3) and (4) or (5)and (6), respectively, are connected to two reactive groups (F_(i)) viaone or two R groups of the series R1-R4 with the other R-group(s)representing a random side chain or hydrogen atoms.

Hence, for formula (3), the structural element (4H) is preferablyconnected to a reactive group (F₁) via R1 and a reactive group (F₁) or(F₂) via R2, whereas R3 is a random side chain or a hydrogen atom; orthe structural element (4H) is connected to a reactive group (F₁) via R1and to a reactive group (F₁) or (F₂) via R3, whereas R2 is a random sidechain or a hydrogen atom; or the structural element (4H) is bonded totwo reactive groups (F_(i)) both via R₁, whereas R2 and R3 are randomside chains or hydrogen atoms. According to the invention, the randomside chain is preferably a C₁-C₇ alkyl group, most preferably2-ethylpentyl or methyl. According the present invention, the term“alkyl” when used in connection with the random side chain encompasseslinear, branched and cyclic alkyl groups but the random side chain ispreferably a linear alkyl group (to indicate that the reactive groups(F_(i)) may be different, they are specified as (F₁) or (F₂)).

Most preferably, for formula (3), one reactive group (F₁) is connectedvia R1 and one reactive group (F₁) or (F₂) is connected via R3, while R2is a random side chain as defined above.

More preferably, for formula (5), the structural element (4H*) isconnected to a reactive group (F₁) via R1 and a reactive group (F₁) or(F₂) via R2, whereas R3 is a random side chain as defined above or ahydrogen atom, or the structural element (4H*) is connected to areactive group (F₁) via R1 and to a reactive group (F₁) or (F₂) via R3,whereas R2 is a random side chain as defined above or a hydrogen atom.Most preferably, for formula (5), one reactive group (F₁) is connectedvia R1 and one reactive group (F₁) or (F₂) is connected via R3, while R2is a random side chain as defined above.

The reactive groups (F_(i)) can comprise any functional group. Preferredfunctional groups, however, are a hydroxy, carboxylic acid, carboxylicester (including activated ester), acid halide, isocyanate (includingblocked isocyanate), thioisocyanate, primary amine (including activatedamine), secondary amine (including activated amine), vinyl,(meth)acrylate, thiol or halogen group.

In this patent application, “hydroxy” denotes a —OH group.

A “carboxylic acid” denotes a —C(O)OH group.

A “carboxylic ester” denotes a —C(O)OR group, wherein R is selected fromthe group consisting of C₁-C₆ alkyl, C₆-C₁₂ aryl, C₇-C₁₂ alkaryl andC₇-C₁₂ alkylaryl groups, wherein the alkyl groups may be linear,branched or cyclic.

An “acid halide” denotes a —C(O)X group, wherein X is a chlorine atom, abromine atom or a iodine atom. Preferably X is a chlorine or a bromineatom.

An “isocyanate” denotes a —NCO group.

A “blocked isocyanate” denotes a —NHC(O)OR* group, wherein R* is a goodleaving group. Suitable examples of good leaving groups arephenol-derivatives phenol and thiophenol derivatives, ester derivativessuch as the methyl ester of hydroxy-benzoic acid, alcohol derivativessuch as 2-ethyl-hexyl-alcohol and t-butyl-alcohol, oxime derivativessuch as methyl-ethyl ketoxime, imidazole groups, caprolactam groups andhydroxy-succinimide groups.

A “thioisocyanate” denotes a —NCS group.

An “blocked thioisocyanate” denotes a —NHC(S)OR* group, wherein R* is agood leaving group as indicated for “blocked isocyanate”.

A “primary amine” denotes a —NH₂ group.

A “secondary amine” denotes a —NHR group, wherein R is as defined abovefor “carboxylic ester”.

An “activated amine” denotes a —C(R)═NOH group (that can be convertedinto an amine group via the Beckmann rearrangement), a —C(O)N₃ group(that can be converted into an amine group via the Curtiusrearrangement), a —C(O)NH₂ group (that can be converted into an aminegroup via the Hofmann rearrangement), a —NHC(O)R group wherein R is asdefined above for “carboxylic ester” including cyclic groups such ascaprolactam, a heterocyclic five or six membered group comprising 1-3heteroatoms selected from the group consisting of O, S and N such asimidazole. According to the present invention, the “activated amine” ispreferably caprolactam or imidazole.

A “vinyl” denotes a —CR^(a)═CR^(b) ₂ group, wherein R^(a) and R^(b) areindependently selected from the group consisting of hydrogen atoms andthe groups defined for R.

A “(meth)acrylate” denotes a —C═C(R^(c))—C(OH)R group, wherein R^(c) isa hydrogen atom or a methyl group and wherein R is as defined above or ahydrogen atom.

A “thiol” denotes a —SH group.

A “halogen” denotes a —X group, where X is chlorine, bromine or iodine.

Preparation of Monomeric Units (a)

According to the invention, the monomeric units (a) are preferablyprepared by the following methods (see also the figures).

Preferred First Method, with X Derived from the Applied di-isocyanate

In the first method, according to formula (3), monomeric unit (a) isobtained by reaction of an isocytosine derivative having an alcoholfunction in the R2 or R3 group with 2 equivalents of a diisocyanatederivative represented by the formula:OCN—X—NCOwherein X is a linear, branched or cyclic C₁-C₁₆ alkyl group, a C₆-C₁₆aryl group, a C₇-C₁₆ alkaryl or a C₇-C₁₆ alkylaryl group.

Preferably, the isocytosine-derivative is a 6-alkyl-isocytosine with analcohol functionality in the R3 group, wherein the alkyl group may bebranched or linear and contains one to seven carbon atoms, morepreferably 5-(2-hydroxyethyl)-6-alkyl-isocytosine, wherein the alkylgroup may be branched or linear and contains one to seven carbon atoms,and most preferably 5-(2-hydroxyethyl)-6-methyl-isocytosine. Examples ofsuitable diisocyanates that can be used in this invention are:

-   1,4-diisocyanato-4-methyl-pentane,-   1,6-diisocyanato-2,2,4-trimethylhexane,-   1,6-diisocyanato-2,4,4-trimethylhexane,-   1,5-diisocyanato-5-methylhexane,-   3(4)-isocyanatomethyl-1-methylcyclohexyl isocyanate,-   1,6-diisocyanato-6-methyl-heptane,-   1,5-diisocyanato-2,2,5-trimethylhexane,-   1,7-diisocyanato-3,7-dimethyloctane,-   1-isocyanato-1-methyl-4-(4-isocyanatobut-2-yl)-cyclohexane,-   1-isocyanato-1 ,2,2-trimethyl-3-(2-isocyanato-ethyl)-cyclopentane,-   1-isocyanato-1 ,4-dimethyl-4-isocyanatomethyl-cyclohexane,-   1-isocyanato-1,3-dimethyl-3-isocyanatomethyl-cyclohexane,-   1-isocyanatol-n-butyl-3-(4-isocyanatobut-1-yl)-cyclopentane.-   1-isocyanato-1,2-dimethyl-3-ethyl-3-isocyanatomethyl-cyclopentane,-   3(4)-isocyanatomethyl-1-methylcyclohexyl isocyanate (IMCI),-   toluene diisocyanate (TDI),-   methylene diphenyl diisocyanate (MDI),-   methylene dicyclohexane 4,4-diisocyanate,-   isophorone diisocyanate (IPDI), hexane diisocyanate (HDI). More    preferably, the diisocyanate is IPDI, HDI, MDI, TDI,    1,6-diisocyanato-2,2,4-trimethylhexane,    1,6-diisocyanato-2,4,4-trimethylhexane or methylene dicyclohexane    4,4-diisocyanate.

Preferred Second and Third Methods, X and Y are Short Alkylene Spacersand the Alkyl Esters are Preferably Methyl or Ethyl

In a second method, according to formula (3), monomeric unit (a) isobtained by reaction of a 6-alcyl-isocytosine bearing a C₁-C₆ carboxylicester in the R3 group with a bifunctional compound that contains anisocyanate or activated amine function and another function.

Preferably, the isocytosine derivative is5-(3-alkyl-propionate)-6-methyl-isocytosine as shown in the reactionequation depicted above and the bifunctional compound is an isocyanatewith C₁-C₆ carboxylic alkyl ester function, wherein the alkyl group maybe branched or linear and contains one to seven carbon atoms. Suitableexamples of such bifunctional compounds are the ethyl ester of1-isocyanato acetic acid, the ethyl ester of 3-isocyanato propionicacid, or the ethyl ester of 6-isocyanato hexanoic acid.

In a third method, according to formula (3), monomeric unit (a) isobtained by reaction of a 6-alkyl-isocytosine bearing a C₁-C₆ carboxylicester in the R3 group and a (masked) isocyanato-function in the R1-groupwith a bifunctional compound that contains a primary amine and anotherfunction, preferably a C₁-C₆ carboxylic alkyl ester or alcohol function.

Preferably, as is schematically shown in the reaction equation depictedabove, the isocytosine derivative is1-carboimidazole-5-(3-ethyl-propionate)-6-methyl-isocytosine, and thebifunctional compound is an alpha-amino-omega-alcohol alkane wherein thealkylene moiety comprises 1-16 carbon atoms and wherein the alkylenemoiety may be linear or branched, or an alpha amino omega carboxylicester alkane wherein the alkylene moiety comprises 1-16 carbon atoms andwherein the alkylene moiety may be linear or branched and wherein theester group is derived from a C₁-C₆ alcohol.

In these second and third methods, X en Y independently denote shortalkylene spacers, wherein the alkylene group is a C₁-C₆ alkylene groupthat may be linear or branched and wherein the alkyl groups of the estermoieties independently denote linear or branched C₁-C₆ alcyl groups,preferably methyl or ethyl groups.

Preferred Fourth Method, X is a Short Alkylene Spacer, F₁ and F₂ areAlcohols or Carboxylic Esters

In a fourth method, according to formula (3), monomeric unit (a) isobtained by first activating an isocytosine, preferably 6-methylisocytosine or 6-(2-ethyl-pentyl)-isocytosine, with a di-substitutedcarbonyl compound, such as for example carbonyl diimidazole (CDI),followed by reaction of the resulting 1-carboimidazole-isocytosine withan amine-compound that contains two additional functions, preferablycarboxylic ester(s) and/or alcohol(s).

Examples of the amine-compound are glutaric acid, aspartic acid,2-amino-2-methyl 1,3-propanediol, 2-amino-1,3-propanediol. In thisfourth method X is defined above and F1 and F2 are independently —OHgroups or ester groups —C(O)OR wherein R is a linear or branched C₁-C₆alkyl group

Preferred Fifth Method, X is an Alkylene Spacer, F1 and F2 are Alcoholsor Carboxylic Esters and Y is a Spacer

In a fifth method, according to formula (3), monomeric unit (a) isobtained by reacting an isocytosine, preferably 6-methyl-isocytosinewith one equivalent of a diisocyanate OCN—X—CNO defined above. Theproduct bearing one isocyanate function is then reacted with anamine-compound or alcohol-compound that bears two further functionsF₁—Y—F₁ or F₁—Y—F₂. An example of such compound isbis(2-hydroxyethyl)amine. According to this fifth method, F₁, F₂, X andY are defined as above.

Preferred Sixth Method, n is 0 or 1, Alkyl is Preferably Methyl or Ethyl

In a sixth method, according to formula (5), monomeric unit (a) is anisocytosine with an alcohol or carboxylic ester function in the R2 or R3group, more preferably in the R3 group, most preferably monomeric unit(a) is 5-(2-hydroxyethyl)-6-methyl-isocytosine or5-(3-ethyl-propionate)-6-methyl-isocytosine. The ester function ispreferably derived from a linear or branched C₁-C₆ alcohol.

Description of the Macromonomeric Unit (b)

Chain Extension Approach

Macromonomeric unit (b) can be any functional polymer or oligomer andcan be represented in the following schematic form:P—(F_(i))_(s)

where P represents the polymer chain, F_(i) represents the functional orcomplementary reactive groups in the macromonomeric unit and srepresents the number of these groups in the macromonomer. Thecomplementary reactive or functional groups (F_(i)) are defined asprevious for monomer (a), s is 1 or more, preferably 2 to 6, morepreferably 2 to 3, most preferably 2, with the proviso that thecomplementary group is complementary reactive with another F_(i) ofmonomeric unit (a).

In this preferred embodiment of the present invention, themacromonomeric unit (b) has a discrete low number of reactive endgroups, most preferably two, so the macromonomeric unit (b) canschematically be written as:F₂—P—F₂ or F₁—P—F₂wherein P represents any polymer backbone, such as a polyether,polyester, polyamide, polyacrylate, polymethacrylate, polyolefin,hydrogenated polyolefin, polycarbonate, or the like. P can alsorepresent copolymers of any kind. According to a preferred embodiment ofthe invention, P is selected from the group consisting of polyether,polyester, polycarbonate or hydrogenated polyolefin. In this approach,the number average molecular weight of the polymer P is preferably inthe range from 100 to 100000, more preferably from 100 to 30000, evenmore preferably 500 to 30000, most preferably from 500 to 5000.

Preferably, macromonomeric unit (b) is a polymer with two hydroxylend-groups. Examples are polyetherdiols having a polyoxyalkylenestructure and hydroxyl end-groups, such as polyethylene glycol,polypropylene glycol, poly(ethylene-co-propylene) glycol,polytetramethylene glycol, or polyesterdiols, such aspolycaprolactonediol, diol end-capped poly(1,4-butylene adipate), diolend-capped poly(1,4-butylene glutarate), or polyolefinediols, such ashydroxyl functionalized polybutadiene, hydroxyl functionalizedpoly(ethylene-butylene), or polycarbonates such as poly(1,3-propanediolcarbonate)glycol or poly(1,6-hexanediol carbonate) glycol, or polyamidediols.

Another preferred macromonomeric unit (b) is a polymer with primaryamine end-groups. Examples are Jeffamines® (polyoxyalkylenea aminesproduced and marketed by Huntsman) and aliphatic polyamides.

Another preferred macromonomeric nit (b) is a polymer with isocyanateend groups. Examples are polymers with hydroxyl end groups (see above)that have been treated with two equivalents of a diisocyanate,preferably isophorone diisocyanate (IPDI).

Yet another preferred macromonomeric unit (b) has vinyl end groups.

Polymer Redistribution Approach

In this embodiment of the invention, the macromonomeric unit (b) has ahigh number of functional groups in the main chain of the polymer. Themacromonomeric unit (b) is a polymer that can be written as:Pwhere P represents polymers or copolymers of any kind, provided they canbe submitted to redistribution reactions with a monomer. Theseredistribution reactions are well known to the skilled person in theart. Reference is for example made to Korshak, V. V. and Vasnev, V. A.,Comprehensive Polymer Science; Pergamon Press; London, 1989; Vol. 5,page 131. In this approach, the number average molecular weight of P isin the range from 5000 to 100000, more preferably from 10000 to 80000.

Examples for P that are well known in the art are polyesters obtained byring-opening polymerization (ROP) of cyclic lactones, glyclides,lactides or mixtures thereof such as polycaprolactone, polylactide,poly(lactide-c-glycolide), aliphatic polyesters obtained by AA-BB typepolycondesation, such as poly(2-methyl-1,3-propylene adipate), oraromatic polyesters such as poly(ethylene terephthalate). According tothe invention, preferred examples for P are polyesters andpolycarbonates.

Description of the Copolymerization and of the Polymer

The polymers presented in this invention are obtainable by reacting orcopolymerizing the disclosed monomeric unit (a) with the disclosedmacromonomeric unit (b), either via the chain extension or theredistribution approach, to a polymer (c). The reactive groups (F_(i))in monomeric unit (a) and the complementary reactive groups (F_(i)) inmacromonomeric unit (b) must be complementary. In this patentapplication complementary reactive groups are to be understood asreactive groups that form, preferably covalent, bonds under conventionalreaction conditions as will be apparent to a person skilled in the art.Examples for complementary reactive groups are carboxyl and hydroxylgroups that can form an ester group, carboxyl and amine groups that canform an amide group, hydroxyl groups that can form an ether group etc.Preferred combinations of reactive groups and complementary reactivegroups (and vice versa) are:

-   -   reactive group=—OH; complementary reactive group=—C(O)OR wherein        R is selected from the group consisting of hydrogen atoms, C₁-C₆        alkyl, C₆-C₁₂ aryl, C₇-C₁₂ alkaryl and C₇-C₁₂ alkylaryl groups,        wherein the alkyl groups may be linear, branched or cyclic, or        wherein OR represents a halogen atom selected from the group        consisting of Cl, Br and I. Suitable examples for R are        pentafluorophenyl, 4-nitrophenyl or 2-nitrophenyl.    -   reactive group is primary or secondary amine of the formula        —NHR, wherein R is selected from the group consisting of        hydrogen atoms, C₁-C₆ alkyl, C₆-C₁₂ aryl, C₇-C₁₂ alkaryl and        C₇-C₁₂ alkylaryl groups, wherein the alkyl groups may be linear,        branched or cyclic; or wherein the primay or secondary amine is        of the formula HRN—(CH₂—CH₂X)_(n)—H wherein R is as defined        herein above, X is independently selected from the group        consisting of O, S and NH and is preferably O, and wherein n is        1-10; complementary reactive group is —NCO.

The polymer product (c) is a segmented copolymer that has structuralelements (4H) in the polymer backbone. For the chain extension approach,polymer (c) can be written as,{(a)_(p)-(b)_(q)}_(v)

wherein ν is the number of repeating units of the connected monomericunit (a) and the connected macromonomeric unit (b).

For the polymer redistribution approach polymer (c′) can be written as,{(a)_(p)-(b′)_(q)}_(w)where (b′) represents the incorporated and fragmented parts ofmacromonomer unit (b), and w is the number of repeating units of theconnected monomeric unit (a) and fragments (b′).

The production of polymers (c) and (c′) may involve any lind ofpolymerization procedure or process known in traditional polymerization.Solution, bulk, suspension, and other types of polymerizations may beused; one-pot procedures or a sequence of (polymerization) reactions maybe used to produce polymers (c) and (c′).

The resulting polymers (c) and (c′) have an number average molecularweight in between 2000 and 80000.

Chain Extension Polymerization

In this embodiment of the invention (i.e. the macromonomeric unit (b) ischain extended) the following sets of monomeric unit (a) andmacromonomeric unit (b) are polymerized:F₁-4H-F₁ and F₃—P—F₃F₁-4H-F₂ and F₃—P—F₃F₁-4H*-F₁ and F₃—P—F₃F₁-4H*-F₂ and F₃—P—F₃where the couple F₁-F₃ and the couple F₂-F₃ are complementary reactivegroups (as defined above), enabling covalent bond formation uponreaction between the two complementary reactive groups. Thecomplementary reactive groups F₁, F₂ and F₃ can be any functional group,examples have been described previously (for F_(i)). However, accordingto the invention it is preferred that F₁, F₂ and F₃ are an isocyanate,blocked isocyanate, alcohol, carboxylic acid or a derivative thereof orprimary or secondary amine as defined above. In a particular embodimentof the invention, monomeric unit (a) contains two isocyanate functions(F₁-4H-F₁, with F₁=isocyanate) and is reacted with macromonomeric unit(b) having two alcohol or two amino functions (i.e. F₃-4H-F₃, F₃=hydroxyor amine). In another particular embodiment of this invention thestructural element (4H) is formed in situ during polymerization byreaction of an isocytosine containing an alcohol-group (i.e. F₁-4H*-F₂,with F₁ is amine and F₂ is alcohol) with a macromoneric unit (b) havingtwo isocyanato functions (i.e. F₃-P-F₃, F₃ =isocyanato).

In another preferred embodiment of this invention monomeric unit (a)containing two carboxylic acid derivative functions (i.e. F₁-4H-F₁ withF₁=carboxylic acid derivative) is reacted with macromonomeric unit (b)having two alcohol or two amine functions (i.e. F₃-P-F₃, F₃=hydroxy oramine).

According to the invention, more than one type of monomeric unit (a)and/or type of macromonomeric unit (b) can be used in the polymerizationreaction. Examples of this inclusion are:

-   (i) The use of two or more macromonomeric units (b) that differ in    number average molecular weight and/or in molecular structure.-   (ii) The use of monofunctional species (‘stopper’-molecules) of    monomeric unit (a) or macromonomeric unit (b); in formulae these    ‘stopper’-molecules can be denoted as: P-F₁ or 4H-F₁ or 4H*-F₁. The    procedure of adding ‘stopper’ molecules is well known in the art    (cf. for example Flory, P. J.; J. Am. Chem. Soc. 1942, Vol. 64, p.    2205), and enables the control of the molecular weight and of the    end-groups in the polymer product (c). A particular ‘stopper’    molecule 4H-F₁ is    2-(3-(6-isocyanato-hexyl)-ureido-6-methyl-isocytosine.-   (iii) The use of branching species of monomeric unit (a) or    macromonomeric unit (b); in formulae these branched molecules can be    denoted as: P-(F_(i))_(u) or 4H-(F_(i))_(u) or 4H*-(F_(i))_(u), with    u being 3 or more up to 6, preferably 3. The use of branched    molecules enables the control of branching in and of molecular    weight of the polymer product (c).

As will be apparent to those skilled in the art, in the followingformula representing the macromonomeric unit (b):P—(F_(i))_(s)s may be zero (redistribution reactions) or s may be 1 if monofunctionalspecies (‘stopper’-molecules) of monomeric unit (a) or macromonomericunit (b) are used.

According to the invention, any molar ratio between monomeric unit (a)and macromonomeric unit (b) can be used in the polymerization reaction.This enables the control of the number average molecular weight of theproduct polymer (c), and of the average amount of structural elements(4H) per polymer chain in polymer (c). Preferred molar ratios betweenmonomeric unit (a) and macromonomeric unit (b) range from 1:2 to 2:1,more preferably ratios from 2:3 to 3:2 are used, and most preferably themolar ratio is 4:5 to 5:4.

The Polymer Redistribution Reaction

In another preferred embodiment of the invention the following sets ofmonomeric units (a) and macromonomeric units (b) are reacted (i.e. thepolymer redistribution reaction):F₁-4H-F₁ and PF₁-4H-F₂ and P

In redistribution, monomeric unit (a) is mixed and reacted withmacromonomeric unit (b). During reaction, both reactive ends ofmonomeric unit (a) react with the chemical bonds in the polymer chain ofmacromonomeric unit (b), so that macromonomeric unit (b) is fragmented—to (b′)— and a new polymer (c′) with structural elements (4H) in itsbackbone is formed. Additionally, fragments of polymer (b) without4H-units are formed.

The reactive groups F₁, and F₂ can be any functional group, exampleshave been described previously (for F_(i)). Particularly, F₁ and F₂ arehydroxy groups, primary or secondary amine groups, carboxylic acidgroups or derivatives thereof, preferably carboxylic ester groups, orcarbonates, while P is a polyester, polycarbonate, polyamide orcopolymers of said polymers P. Preferably, the monomeric units comprise—OH groups as reactive groups whereas the polymer P comprises ascomplementary reactive groups a carboxylic acid, a carboxylic acidanhydride, a carboxylic halide (halide preferably Cl or Br), acarboxylic ester or an activated ester group as defined above; or themonomeric units comprise carboxyl ester groups as defined above whereasthe polymer P comprise as complementary reactive groups a carboxylicacid, a carboxylic halide (halide preferably Cl or Br) or a carboxylicacid anhydride as defined above (carboxylic halides are herein definedas carboxylic acid halides of the formula —C(O)X wherein X is Cl, Br, orI, preferably Cl or Br; carboxylic anhydride are herein defined as—C(O)—O—(O)—C—).

The molar ratio between monomeric unit (a) and macropolymeric unit (b)is in between 3:1 and 10:1, more preferably in between 5:1 and 8:1. Thenumber molecular weight of (b) is in between 20000 and 100000.

In a preferred embodiment of this invention redistribution takes placeby transesterfication reactions between monomeric unit (a) wherein F₁ orF₂ is an alcohol, carboxylic acid, or carboxylic ester function andmacromonomeric unit (b) is a polyester or a polycarbonate. Thetransesterfication can take place in the presence of catalysts welllmown in the art such as metal-based catalysts, for example titanium ortin compounds, or metal-free organic catalysts, for example DMAP orN-heterocyclic carbenes. Or the transesterfication can be catalyzed byenzymes such as lipases, preferably Candida antarctica lipase Bimmobilized on resin (for example sold as Novozyme-435 by Novozyme,Denmark). Enzymatic transesterfication are especially beneficial inembodiments of this invention that are applied in (bio)medical orcosmetic applications that require complete absence of any residualmetal catalyst.

Alternatively, both copolymerization procedures (i.e. chain extensionand redistribution) may be combined to obtain polymers according to theinvention.

Applications

The copolymers according to the invention are in particular suitable forapplications related to personal care (hair preparations, skin cosmeticsand laundry aids), surface coatings (leather, textile, optical fibers,paper and paint formulations), imaging technologies (printing,stereolithography, photography and lithography), biomedical applications(materials for controlled release of drugs and materials fortissue-engineering, tablet formulation), (thermo)reversible coatings,adhesive and sealing compositions, and thickening agents, gelling agentsand binders.

EXAMPLES

The following non-limiting examples further illustrate the preferredembodiments of the invention. When not specifically mentioned, chemicalsare obtained from Aldrich.

Building Blocks

A mixture of methylisocytosine (10 g) and carbodiimidazole (CDI; 20.7 g)in dried DMSO (50 mL) was heated and stirred at 100° C. under an argonatmosphere for 2 hours. The resulting solid was filtered after coolingand washed with dry acetone until a white powder remained in the filter,that subsequently was dried in vacuo and stored over P₂O₅. FT-IR (neat):ν (cm⁻¹) 3174, 1701, 1644, 1600, 1479, 1375, 1320, 1276.

1,6-Hexyldiisocyanate (650 g) and methylisocytosine (or2-amino-4-hydroxy-6-methyl-pyrimidine, 65.1 g) were suspended in a2-liter flask. The mixture was stirred overnight at 100° C. under anargon atmosphere. After cooling to room temperature, a liter of pentanewas added to the suspension, while stirring was continued. The productwas filtered, washed with several portions of pentane and dried invacuum. A white powder was obtained. ¹H NMR (400 MHz, CDCl₃): δ 13.1(1H), 11.8 (1H), 10.1 (1H), 5.8 (1H), 3.3 (4H), 2.1 (3H), 1.6 (4H), 1.4(4H). FT-IR (neat): ν (cm⁻¹) 2935, 2281, 1698, 1668, 1582,1524, 1256.

Methylisocytosine (5.2 g) was added to isophoronediisocyanate (IPDI, 50mL) and subsequently stirred at 90° C. under an argon atmosphere for 3days. The resulting clear solution was precipitated in heptane. Thewhite gum was collected, heated in 150 mL heptane, cooled on ice, andfiltered. The same procedure was repeated once more with the whiteresidue, resulting in a white powder. ¹H NMR (400 MHz, CDCl₃): δ 13.1(1H), 12.0 (1H), 10.1 (1H), 5.9 (1H), 4.1-3.1 (3H), 2.1 (3H), 2.0-0.9(15H). FT-IR (neat): ν (cm⁻¹) 2954, 2255, 1696, 1662, 1582, 1524, 1247.The product exists in four different isomers: two regio-isomers, one ofwhich is shown above, exist in cis and trans configuration. For reasonsof clarity, only one isomer is shown.

Synthesis of Monomer (a) Compounds

2-Acetylbutyrolactone (2 mL) and guanidine carbonate (3.3 g) were put toreflux in absolute ethanol (20 mL) in the presence of triethylarnine(5.2 mL). The solution became yellow and turbid. After overnight heatingat reflux, the solid was filtered, washed with ethanol, and suspended inwater. The pH was adjusted to a value of 6-7 with an HCl-solution, andthe mixture was stirred for a while. Filtration, rinsing of the residuwith water and ethanol and subsequent drying of the solid gave the pureproduct.

¹H NMR (400 MHz, DMSO-d₆): δ 11.2 (1H), 6.6 (2H), 4.5 (1H), 3.4 (2H),2.5 (2H), 2.1 (3H). FT-IR (neat): ν (cm³¹ ¹) 3333, 3073, 2871, 1639,1609, 1541, 1487, 1393, 1233, 1051, 915, 853, 789, 716.

A mixture of guanidine carbonate (20 gram), diethyl-2-acetylglutarate(12 mL) and ethanol (100 mL) was put to reflux during 24 hours. Thevolatiles were removed by evaporation, the remaining solids weredissolved in cold water and the solution was acidified to ca. pH=6. Thesuspension was stirred for a few minutes and filtered. The residu waswashed with some water, then with ethanol and was dried in a vaccuumstove. Yield: 61%. ¹H NMR (400 MHz, DMSO-d₆): δ 6.8 (2H), 4.0 (2H), 2.5(2H), 2.4 (2H), 2.1 (3H), 1.2 (3H).

Monomer a1 (1 g) was suspended in 1,6-hexyldiisocyanate (12 mL) andpyridine (1 mL) and was stirred at 90° C. A clear solution developed,and thereafter some gel particles formed (unwanted). The solution wascooled and filtered through some celite. The filtrate was dropped intopentane giving a white precipitate. This precipitate was again stirredin pentane to remove the last traces of 1,6-hexyldiisocyanate. Isolationvia filtration was followed by drying, giving the pure diisocyanate. ¹HNMR (400 MHz, CDCl₃): δ 13.1 (1H), 11.9 (1H), 10.2 (1H), 4.8-4.6 (1H),4.2 (2H), 3.3 (6H), 3.1 (2H), 2.7 (2H), 2.3 (3H), 1.7-1.2 (16H). FT-IR(neat): ν (cm⁻¹) 3314, 2936, 2263, 1688, 1662, 1640, 1590, 1535, 1444,1257, 1140, 1025, 780, 742.

Monomer a1 (12 gram) was suspended in IPDI (150 mL) and was stirredovernight at 90° C. under an argon atmosphere. A clear solutiondeveloped. The solution was cooled and precipitated in hexane. The solidwas filtered, stirred in another portion of hexane, and then the productwas isolated by filtration, washing with hexane and drying of theresidu. Yield: 98%. ¹H NMR (400 MHz, CDCl₃): δ 13.1 (1H), 11.9 (1H),10.2 (1H), 4.8-4.5 (1H), 4.2 (2H), 4.0-3.2 (3H), 3.1-2.9 (3H), 2.7 (2H),2.3 (3H), 1.9-1.6 (4H), 1.4-0.8 (26H). FT-IR (neat): ν (cm⁻¹). 2954,2254, 1690, 1664, 1637, 1590, 1532, 1461, 1364, 1307, 1257, 1034, 791.MALDI-TOF-MS, [M⁺]=614, [M+Na⁺]=636. For convenience, only one isomer ofthe product is shown. IPDI exists in different regio- and stereoisomers,and the coupling is not selective for one of the isocyanate functions inIPDI.

Monomer a2 (7.1 g), carbodiimidazole (8.23 g; CDI) and DMF (50 mL) werestirred under an argon atmosphere at an oil bath temperature of 100° C.The mixture became clear during the 3 hours reaction time. Cooling andaddition of dry acetone induced precipitation. The residu was washedwith acetone and dried. ¹H NMR (300 MHz, DMSO-d₆): δ 8.3 (1H), 7.6 (1H),7.0 (1H), 6.6 (2H), 4.0 (2H), 2.5 (2H), 2.4 (2H), 2.1 (3H), 1.2 (3H).

Monomer a5 and 6-amino-1-hexanol were mixed in equimolar amounts inchloroform. The mixture was refluxed and became clear during theovernight reaction that was executed under an argon atmosphere. Thesolution was extracted with an aqueous NaCl solution and with water, andwas then dried with Na₂SO₄. Precipitation in hexane gave a white solid.¹H NMR (300 MHz, CDCl₃): δ 13.0 (1H), 11.9 (1H), 10.1 (1H), 4.9 (1H),4.1 (2H), 3.7 (2H), 3.3 (2H), 2.7 (2H), 2.6 (2H), 2.3 (3H), 1.6 (4H),1.4 (4H), 1.3 (3H).

Triethylamine (1.6 mL) was added to a suspension of the HCl-salt ofL-serine (1.56 gram) in dry chloroform (25 mL). The isocyanate buildingblock 2 (2.95 g) was added and the mixture was stirred overnight at 60°C. under an argon atmosphere. The precipitate was first stirred inCHCl₃, filtered and washed and then this procedure was repeated inethanol. The yield of the dried powder product was 80%. ¹H NMR (300 MHz,DMSO-d₆): δ 10.6 (1H), 7.6 (1H), 6.6 (1H), 6.3 (1H), 6.2 (1H), 5.7 (1H),5.1 (1H), 4.2 (1H), 3.8-3.3 (5), 3.1 (2H), 3.0 (2H), 2.1 (3H), 1.5-1.2(8H). FT-IR (neat): ν (cm⁻¹) 3329, 2936, 2605, 1736, 1703, 1659, 1623,1567, 1525, 1436, 1253, 1036, 741.

Diethanolamine (1.33 g) and the isocyanate building block 2 (3.7 g) weremixed in 30 mL THF. The suspension was put to reflux under an argonatmosphere during 20 hours. The suspension was filtered after coolingdown, the residu was washed with THF and the yellow waxy compound wasdried. Yield 86%. ¹H NMR (300 MHz, DMSO-d₆): δ 10.7 (1H), 7.7 (1H), 6.7(1H), 6.3 (1H), 5.7 (1H), 4.8 (2H), 3.5 (4H), 3.3(4H), 3.2 (2H), 3.0(2H), 2.1 (3H), 1.5-1.2 (8H). FT-IR (neat): ν (cm⁻¹) 3324, 3212, 2930,1698, 1662, 1584, 1526, 1253, 1074, 765, 740.

The hydrogen chloride acid of L-glutamic acid diethylester (1.02 g) wasdissolved in 15 mL THF in the presence of 0.65 mL triethylamine. To thissolution building block 1 was added and subsequently stirred under anargon atmosphere. After 20 hours, acetone (15 mL) was added and themixture was subsequently filtered. The residu was washed with acetoneand the white powder was dried in vacuo. Yield 82%. ¹H NMR (300 MHz,DMSO-d₆): δ 7.1 (1H), 5.8 (1H), 4.4 (1H), 4.2-4.0 (4H), 3.1 (4H), 2.1(3H), 1.2 (6H). FT-IR (neat): ν (cm⁻¹) 2938, 2603, 1753, 1731, 1699,1668, 1638, 1591, 1529, 1261, 1208, 1027, 805.

2-Amino-1,3-propanediol (0.54 g) was added to building block 1 (2.2 g)were mixed in 15 mL THF. The suspension was stirred at room temperatureunder an argon atmosphere during 20 hours. The solution was subsequentlywashed three times with water, dried on sodium sulphate. The productcrystallized from a concentrated solution, and was subsequently isolatedaw a white powder by filtration. Yield 63%. ¹H NMR (300 MHz, DMSO-d₆): δ10.7 (1H), 7.7 (1H), 5.7 (1H), 5.0-4.8 (1H), 3.8-3.4 (8H), 2.3 (1H),1.8-1.1 (7H), 0.8 (6H). FT-IR (neat): ν (cm⁻¹) 3214, 2930, 1694, 1646,1557, 1526, 1457, 1243, 1048, 765.

Monomer a2 (1.23 g) was dispersed in 10 mL THF, followed by the dropwiseaddition of ethyl 6-isocyanatohexanoate (1.2 mL). The suspension was putto reflux under an argon atmosphere during 20 hours. The suspension wasfiltered after cooling down, the residu was washed with THF and thewhite powder was isolated and dried in vacuo. Yield 92%. ¹H NMR (400MHz, CDCl₃): δ 12.9 (1H), 11.9 (1H), 10.2 (1H), 4.2 (2H), 3.3 (2H), 2.7(2H), 2.6 (211), 2.3 (3H), 1.7 (4H), 1.4 (2H), 1.2 (3H). FT-IR (neat): ν(cm⁻¹) 3214, 2982, 1729, 1698, 1661, 1642, 1584, 1264, 1188, 787.

Synthesis of Polymers (c) and (c′)

Telechelic PEO-1500 (5.83 g) was stripped three times with toluene andwas then dissolved in toluene (30 mL). Monomer a4 (2.39 g) in toluene(14 mL) was added as well as a few drops of dibutyl tin dilaurate andthe solution was heated overnight under argon (oil bath temperature of120° C.). The polymer was isolated by precipitation into diethylether.The material is white (semi-crystalline), elastic and tough. ¹H NMR (300MHz, CDCl₃/CD₃OD): δ 4.1, 3.6, 2.8, 2.2, 1.8-1.4, 1.2-0.8. SEC (THF,PS-standards): M_(w)=7.0 kD.

Acclaim-2220, a telechelic random co-polymer of ethylene oxide andpropylene oxide with an average molecular weight of ca. 2.2 kD (3.81 g,a product of Bayer, Germany), monomer a4 (1.05 g) and a drop of dibutyltin dilaurate were mixed in toluene (10 mL) and pyridine (1 mL) and thesolution was stirred overnight under argon at an oil bath temperature of120° C. The product was isolated by evaporation of the solventsprecipitation into hexane. The material is a colourless, elasticmaterial.

¹H NMR (300 MHz, CDCl₃/MeOH): δ 5.4-4.8, 4.4-3.2, 2.9, 2.4-2.0, 1.7,1.5-0.6. SEC (THF, PS-standards): M_(n)=12.1 kD, D=1.6.

Kraton L2203 (11.2 g, a product of Kraton Polymers, USA), a telechelicalcohol terminated polybutylene/ethylene, in 20 mL of chloroform wasadded drop wise to a solution of IPDI (1.46 g) and a few drops ofdibutyl tin dilaurate in chloroform (5 mL). Overnight stirring underargon was followed by heating of the solution at 40° C. for an hour. Thesolvent was removed by evaporation, pyridine (25 mL) and monomer al(0.56 g) were added and the resulting mixture was stirred overnight atan oil bath temperature of 90° C. The pyridine was evaporated and thepolymer was isolated by precipitation from chloroform/ethanol 10:1 intomethanol, and consecutive drying of the solid. The precipitated polymeris a white, soft and elastic material. ¹H NMR (300 MHz, CDCl₃): δ 4.1,3.8, 3.0, 2.8, 2.3, 1.5-0.8. SEC (THF, PS-standards): M_(n)=19.7kD,D=2.1.

Telechelic hydroxy terminated polycaprolacton with a molecular weight of2.0 kD (9.73 g), monomer a4 (2.5 g) and a few drops of dibutyl tindilaurate were dissolved in chloroform (100 mL) and stirred overnight atan oil bath temperature of 60° C. The next day the chloroform wasevaporated, toluene (100 mL) and pyridine (20 mL) were added, as well asa second portion of monomer a4 (0.5 g). The mixture was heated at an oilbath temperature of 120° C. for another night, and the polymer productwas isolated by evaporation of the pyridine, precipitation fromchloroform/methanol 10:1 into methanol and drying of the solid. Uponstanding the material develops into a white (semi-crystalline), elasticpolymer. ¹H NMR (300 MHz, CDCl₃): δ 12.0, 10.1, 4.5-3.8, 3.0, 2.6-2.2,2.0-0.8. SEC (THF, PS-standards): M_(n)=38.5 kD, D=2.0.

A range of chain extended poly(2-methyl-1,3-propylene adipate) polymershave been prepared by reacting a hydroxy functionalized telechelicpoly(2-methyl-1,3-propylene adipate) with monomer a4 in different molarratios. In all cases an excess of polyester has been used and thisexcess determines the average molecular weight and the average number ofquadruple hydrogen bonds in the backbone of the polymer product.Optionally, the hydroxy groups remaining in the polymer product can becapped with building block 3.

Typical procedure (polymer c5-c): Telechelic poly(2-methyl-1,3-propyleneadipate) (average molecular weight Mn=2.0 kD, hydroxy end groups, 5.0 g)was stripped three times with toluene and dissolved in chloroform (25mL) together with monomer a4 (1.16 g) and few drops dibutyl tindilaurate. The mixture was boiled overnight. The next day, the absenceof isocyanate functions was checked using FT-IR spectroscopy, therequired amount of building block 3 (0.46 g) was added and the solutionwas put to reflux for another night. Again, it was verified with FT-IRwhether the isocyanate-functions had disappeared, and the polymer wasisolated by precipitation from a chloroform/methanol solution into etherand drying of the solid. If the reaction mixture became too viscous, drychloroform or THF solvent was added. Typical NMR (polymer c10-a): ¹H NMR(300 MHz, CDCl₃): δ 12.0-11.8, 10.1-9.8, 5.8, 5.0-4.6, 4.3-3.8, 3.4-2.8,2.5-2.0, 1.9-1.6, 1.40.8.

The following table lists the prepared poly(2-methyl-1,3-propyleneadipate) polymers, polymers c5-a-c5-d have been capped with buildingblock 3, while polymers c5-e -c5-h have not been capped (i.e. R=H).

Amount of Building Theoretical Theoretical telechelic Amount of block 34H-units per mol. Measured polyester a4 (g; (g; polymer chain weight MnM_(n) and D Polymer (g; mmol) mmol) mmol) (average) (kg/mol) (SEC)* c5-a9.27; 4.64 1.42; 2.31 1.61; ca. 3 5.3 5.3; 1.8 4.64  c5-b 4.95; 2.481.01; 1.65 0.60; ca. 4 7.9 7.2; 2.0 1.73  c5-c 5.02; 2.51 1.16; 1.890.46; ca. 5 10.5 10.2; 1.9  1.32  c5-d 5.48; 2.74 1.35; 2.19 0.40; ca. 613.1 9.3; 2.3 1.15  c5-e 5.55; 2.78 1.13; 1.84 — ca. 2 7.2 5.6; 2.6 c5-f5.32; 2.66 1.31; 2.14 — ca. 4 12.5 15.5; 1.7  c5-g 10.05; 5.03  3.08;5.02 — infinite infinite  74; 2.1 *Using THF as eluent, UV-detection andapplying polystyrene standardsPolymer c6: Chain Extended poly(caprolactone)

Telechelic hydroxy terminated polycaprolacton with a molecular weight of2.0 kD 10 (9.22 g), was stripped three times with toluene and dissolvedin chloroform (50 mL) together with monomer a4 (2.26 g) and few dropsdibutyl tin dilaurate. The mixture stirred overnight at 60° C., followedby confirming the absence of isocyanate functions with FT-IRspectroscopy. Building block 3 (0.67 g) was added and the solutiondiluted with 25 mL chloroform and put to reflux for another night.Again, it was verified with FT-IR whether the isocyanate-functions haddisappeared, and the polymer was isolated by precipitation from achloroform/ethanol solution into hexane and drying of the solid.

¹H NMR (300 MHz, CDCl₃): δ 12.0, 10.1, 4.5-3.8, 3.0-2.8, 2.6-2.2,2.0-0.8. SEC (THF, PS-standards): M_(n)=11.5 kD, D=2.0.

Polymer c7: Copolymer with poly(2-methyl-1,3-propylene adipate) andpolycaprolactone-blocks

A mixture of telechelic hydroxy terminated poly(2-methyl-1,3-propyleneadipate) with an average molecular weight of 2.0 kD (2.39 g) andtelechelic hydroxy terminated polycaprolactone with an average molecularweight of 2.0 kD (2.39 g), was stripped three times with toluene anddissolved in chloroform (25 mL) together with monomer a4 (1.18 g) andfew drops dibutyl tin dilaurate. The mixture stirred overnight at 60°C., followed by confirming the absence of isocyanate functions withFT-IR spectroscopy, building block 3 (0.35 g) was added and the solutiondiluted with 20 mL chloroform and put to reflux for another night.Again, it was verified with FT-IR whether the isocyanate-functions haddisappeared, and the polymer was isolated by precipitation from achloroform/ethanol solution into hexane and drying of the solid. ¹H NMR(300 MHz, CDCl₃): δ 13.2-12.8, 12.1-11.8, 10.2-9.8, 5.8, 5.2-4.5,4.4-3.6, 3.4-2.6, 2.6-2.0, 2.0-0.6. SEC (THF, PS-standards): M_(n)=12.2kD, D=2.0.

Polymer c8: Mixture of Chain Extended Polycaprolactone andpoly(2-methyl-1,3-propylene adipate)

Polymer c6 (2.2 g) and polymer c5-c (2.2 g) were dissolved in a hotmixture of 20 mL chloroform and 5 mL ethanol. The resulting viscoussolution was poured into a mold and subsequently dried at atmosphericpressure, giving an elastic transparent film.

Polymer c9: Polycaprolactone Resditributed with 4H-unit

Polycaprolactone with a molecular weight of 10 kD (0.35 g), was strippedthree times with toluene. To this polymer was added monomer a6 (76 mg)and toluene (10 mL) in a Schlenck-flask in a nitrogen atmosphere.Subsequently, Novozym 435 (37 mg, immobilized C. antarctica lipase B aproduct from Novo Nordisk, Denmark) was added and the mixture was heatedto 90° C. After stirring for 18 hours, the reaction mixture was dilutedwith chloroform (10 mL), filtered, concentrated and precipitated inmethanol, resulting in a white fiber like material after drying of thesolid. ¹H NMR (400 MHz, CDCl₃): δ 12.9, 11.9 10.2, 4.3-3.8, 3.7, 3.3,2.7, 2.6, 2.4-2.2, 1.9-1.2. SEC (THF, PS-standards): M_(n)13.5 kD,D=1.5.

Enhanced Material Properties of chain-extended polyesters.

The following table shows the enhancement in material propertiesobtained for different polymers after chain extension with the 4H-unit.The resulting polymers c5-d, c6, c7, and c8, all show pronounced elasticbehavior, whereas the non-chain extended polyesters display no elasticbehavior, i.e. the starting poly(2-methyl-1,3-propylene adipate) is aliquid, and the starting polycaprolactone is a brittle crystallinematerial.

Polymer T_(g) (° C.) T_(m) (° C.)^(a) E_(mod) ^(a,b) c5-d −38 — 1.6 c6−46 49 19.3 c7 −43 — 1.7 c8 −46 — 2.9 ^(a)measured on pristine samples^(b)Elastic modulus E_(mod) is measured according to DIN 53 457/1987

1. A supramolecular polymer comprising quadruple hydrogen bonding units within the polymer backbone, wherein at least a monomer comprising a 4H-unit is incorporated in the polymer backbone via at least two to four reactive groups, and the 4H-units are incorporated in the polymer backbone by two covalent bonds, wherein the monomeric unit (a) has a structure according to formula (III) or (IV): 4H-(F_(i))_(r tm (III)) 4H*-(F_(i))_(r)   (IV) wherein F_(i) comprises a reactive group linked to the 4H-unit or 4H*-unit; and r is2; wherein the monomeric unit (a) is represented by formula (VIa):

wherein: the 4H-unit is connected to a reactive group (F₁) via R₁ and a reactive group (F₁) or (F₂) via R₂, whereas R₃ is a random side chain or a hydrogen atom, the random side chain being a linear, cyclic or branched alkyl group comprising 1 to 7 carbon atoms; or the 4H-unit is connected to a reactive group (F₁) via R₁ and to a reactive group (F₁) or (F₂) via R₃, whereas R₂ is a random side chain or a hydrogen atom, the random side chain being a linear, cyclic or branched alkyl group comprising 1 to 7 carbon atoms; or the 4H-unit is connected to two reactive groups (F_(i)) both via R₁, whereas R₂ and R₃ are random side chain or hydrogen atoms, the random side chains being a linear, cyclic or branched alkyl group comprising 1 to 7 carbon atoms; and wherein the monomeric unit (a) is represented by formula (VIIa):

wherein: the 4H-unit is connected to a reactive group (F₁) via R₁ and a reactive group (F₁) or (F₂) via R₂, whereas R₃ is a random side chain or a hydrogen atom, the random side chain being a linear, cyclic or branched alkyl group comprising 1 to 7 carbon atoms; or the 4H-unit is connected to a reactive group (F₁) via R₁ and to a reactive group (F₁) or (F₂) via R₃, whereas R₂ is a random side chain or a hydrogen atom, the random side chain being a linear, cyclic or branched alkyl group comprising 1 to 7 carbon atoms; and wherein R₁-R₃ are selected from the group consisting of hydrogen atoms and shorter or longer chains, the longer and shorter chains being selected from the group consisting of saturated or unsaturated, branched, cyclic or linear alkyl chains, aryl chains, alkaryl chains, arylalkyl chains, ester chains or ether chains.
 2. The supramolecular polymer according to claim 1 comprising quadruple hydrogen bonding units in the polymer backbone, said supramolecular polymer (c) and (c′) having a structure according to formula (I) or formula (II), respectively: {(a)_(p)-(b)_(q)}_(v)   [I] {(a)_(p)-(b′)_(q)}_(w)   [II] wherein: (a) is a monomeric unit that comprises a precursor of a 4H-element; (b) is a macromonomeric unit; (b′) is a fragmented part of the original polymer (b); (a) and (b) are covalently connected, in the polymer backbone; p and q indicate the total number of units of (a) and (b) or (a) and (b′) in the polymer backbone; p is 1 to 100; q is 0 to 20; v is the number of repeating units of the connected monomeric units (a) and the connected macromonomeric units (b); w is the number of repeating units of the connected monomeric units (a) and the connected macromonomeric units (b′); macromonomeric unit (b) has a number average molecular weight of at least about 100 to about 100,000; macromonomeric unit (b′) has a number average molecular weight of at least about 50 to about 20,000; polymer (c) has a number average molecular weight of about 2,000 to about 80,000; polymer (c′) has a number average molecular weight of about 2,000 to about 80,000.
 3. The supramolecular polymer according to claim 2, wherein the macromonomeric unit (b) comprises two to six complementary reactive groups.
 4. The supramolecular polymer according to claim 2, wherein the amount of 4H-units incorporated in the polymer backbone is about 33 to about 66 mol %, based on the total amount of moles of (a) and (b) or (a) and (b′).
 5. The supramolecular polymer according to claim 2, wherein the macromonomeric unit (b) is represented by formula (V): P—(F_(i))_(s)   (V) wherein: P represents a polymer chain having a number average molecular weight of 100 to 100,000; F_(i) represents a complementary reactive group in the macromonomeric unit (b) that is complementary reactive with another F_(i) of monomeric unit (a); and s represents the number of these groups in the macromonomer and is 0-6.
 6. The supramolecular polymer according to claim 2, wherein the macromonomeric unit (b) has a structure according to formula (VIII): F2-P-F2 or F1-P-F2   (VIII) wherein: P is selected from the group consisting of polyesters, polyether, polycarbonates and hydrogenated polyolefins; and F₁ and F₂ are independently selected from the group consisting of —OH, —NH₂, —NCO and —C═CH₂.
 7. The supramolecular polymer according to claim 6, wherein P has a number average molecular weight of 100 to 100,000.
 8. The supramolecular polymer according to claim 6, wherein P has a number average molecular weight of 5,000 to 100,000.
 9. process for the preparation of a supramolecular polymer comprising quadruple hydrogen bonding units within the polymer backbone, wherein at least a monomer comprising a 4H-unit is incorporated in the polymer backbone via at two to four reactive groups, and the 4H-units are incorporated in the polymer backbone by two covalent bonds, the process comprising: reacting a monomeric unit (a) having a structure according to formulae (III) or (IV) with a macromonomeric unit (b) having a structure according to formulae (V) wherein the monomeric unit (a) has a structure according to formula (III) or (IV): 4H-(F_(i))_(r)   (III) 4H*-(F_(i))_(r)   (IV) wherein F_(i) comprises a reactive group linked to the 4H-unit or 4H*-unit; and r is
 2. wherein the monomeric unit (a) is represented by formula (VIa):

wherein: the 4H-unit is connected to a reactive group (F₁) via R₁ and a reactive group (F₁) or (F₂) via R₂, whereas R₃ is a random side chain or a hydrogen atom, the random side chain being a linear, cyclic or branched alkyl group comprising 1 to 7 carbon atoms; or the 4H-unit is connected to a reactive group (F₁) via R₁ and to a reactive group (F₁) or (F₂) via R₃, whereas R₂ is a random side chain or a hydrogen atom, the random side chain being a linear, cyclic or branched alkyl group comprising 1 to 7 carbon atoms; or the 4H-unit is connected to two reactive groups (F_(i)) both via R₁, whereas R₂ and R₃ are random side chain or hydrogen atoms, the random side chains being a linear, cyclic or branched alkyl group comprising 1 to 7 carbon atoms; and wherein the monomeric unit (a) is represented by formula (VIIa):

wherein: the 4H-unit is connected to a reactive group (F₁) via R₁ and a reactive group (F₁) or (F₂) via R₂, whereas R₃ is a random side chain or a hydrogen atom, the random side chain being a linear, cyclic or branched alkyl group comprising 1 to 7 carbon atoms; or the 4H-unit is connected to a reactive group (F₁) via R₁ and to a reactive group (F₁) or (F₂) via R₃, whereas R₂ is a random side chain or a hydrogen atom, the random side chain being a linear, cyclic or branched alkyl group comprising 1 to 7 carbon atoms; and wherein R₁-R₃ are selected from the group consisting of hydrogen atoms and shorter or longer chains, the longer and shorter chains being selected from the group consisting of saturated or unsaturated, branched, cyclic or linear alkyl chains, aryl chains, alkaryl chains, arylalkyl chains, ester chains or ether chains.
 10. The process according to claim 9, wherein the monomeric unit (a) and macromonomeric unit (b) are selected from the group consisting of: F₁-4H-F₁ and F₃-P-F₃; F₁-4H-F₂ and F₃-P-F₃; F₁-4H*-F₁ and F₃-P-F₃; and F₁-4H*-F₂ and F₃-P-F₃ wherein F₁-F₃ and F₂-F₃ are complementary reactive groups.
 11. The process according to claim 9, wherein the reactive groups F_(i) are selected from the group consisting of —NH₂, —NHR, —NCO, blocked —NCO, —OH, —C(O)OH, and —C(O)OR wherein R is a linear or branched C₁-C₆ alkyl group, a C₆-C₁₂ arylgroup, a C₇-C₁₂ alkaryl group or a C₇-C₁₂ alkylaryl group, or R is halogen atom selected from the group consisting of Cl, Br and I.
 12. The process according to claim 9, comprising two or more macromonomeric units (b) each having a different number average molecular weight.
 13. The process according to claim 9, comprising two or more macromonomeric units (b) each having a different molecular structure.
 14. The process according to claim 9, wherein the monomeric unit (a), the macromonomeric unit (b), or both comprises a stopper moiety having the formula P-F₁, 4H-F₁ of 4H*-F₁.
 15. The process according to claim 9, wherein the monomeric unit (a) or the macromonomeric unit (b) comprise branching species, said branching species having the formula P-(F_(i))_(u) or 4H-(F_(i))_(u) or 4H*-(F_(i))_(u), wherein u is an integer between 3 and
 6. 16. The process according to claim 9, wherein the molar ratio between monomeric unit (a) and macromonomeric unit (b) is between about 1:2 and about 2:1.
 17. The process according to claim 9, wherein monomeric unit (a) and macromonomeric unit (b) are selected from the group consisting of: F₁-4H-F₁ and P; and F₁-4H-F₂ and P.
 18. The process according to claim 17, wherein P has an number average molecular weight of between 5,000 and 100,000.
 19. The process according to claim 17, wherein the molar ratio between monomeric unit (a) and macromonomeric unit (b) is between about 3:1 and about 10:1.
 20. A product comprising a supramolecular polymer according to claim 1, in which the product is for personal care, surface coating, imaging technology, biomedical application, (thermo)reversible coating, adhesive, sealing composition, thickening agent, gelling agent or binder.
 21. The supramolecular polymer according to claim 2, wherein (a) and (b) are connected covalently in the polymer backbone.
 22. The supramolecular polymer according to claim 1, wherein the monomeric unit (a) is


23. The process according to claim 9, wherein the monomeric unit (a) is


24. The process according to claim , wherein the monomeric unit (a) is 